Abstract

Description

由氨基羧酸化合物制备聚酰胺的方法 By the method of amino acid compounds prepared polyamide

本发明涉及由氨基羧酸化合物制备聚酰胺的方法、所得的聚酰胺及其用途。 The present invention relates to a method of aminocarboxylic acid compound for preparing a polyamide, the resulting polyamide and their use.

聚酰胺不仅可以由己内酰胺来制备，而且可特别地由氨基己腈来制备。 The polyamide can not only be prepared from caprolactam, and may in particular be prepared from aminocapronitrile.

US 2,245,129描述一种由氨基己腈(“ACN”)与水分批两步制备聚己内酰胺的方法，其温度范围为150至300℃，其由作为所添加的水量的函数的特定温度程序控制，压力不大于30巴。 US 2,245,129 describes a process for the aminocapronitrile ( "ACN") and water the batch prepared in two steps polycaprolactam, at a temperature range of 150 to 300 ℃, the particular temperature program controlling the function of water by as added pressure not more than 30 bar.与由己内酰胺制备的聚己内酰胺相比，此方法的缺点为反应时间长(第一步为20小时)，所形成聚己内酰胺粘度低以及高含量的挥发性碱(基本上为伯酰胺类)。 Compared with polycaprolactam prepared from caprolactam, drawback of this method is the long reaction time (the first step was 20 hours), low polycaprolactam viscosity and volatile base high levels (essentially primary acid amides) are formed.

US 4,568,736通过使用含磷与含硫催化剂解决一部分US2,245,129所述问题。 US 4,568,736 solve the portion US2,245,129 problem by using a phosphorus and a sulfur-containing catalyst.使用这些催化剂改善US 2,245,129所述方法的低时空收率。 Using these catalysts to improve the low space-time yield in US 2,245,129 process.但是，此方法制得的所有产物中挥发性碱的量仍然太高，因此难以处理该聚酰胺，而且其羧基端基数减少。 However, the amount of all the products obtained by this method in the volatile base is still too high, it is difficult to process the polyamide, but also reduce the carboxyl end groups.该方法产物中的氨基与羧基端基间的化学当量差异决定其聚合度不足以及回火期间分子量缓慢增加。 Stoichiometric differences between the amino and carboxyl end groups which product is determined insufficient degree of polymerization and the molecular weight gradually increased during tempering.

此外，几乎不可能完全去除该催化剂，以致于使用该催化剂制得的聚合物的化学与物理性质诸如端基种类与数量或纺丝期间的急变情形受到负面影响。 In addition, almost impossible to completely remove the catalyst, so that the use of chemical and physical properties of the polymer such that the resulting catalyst type and quantity of end groups or blast crisis situation during spinning adversely affected.

本发明目的是提供一种用以制备聚酰胺而且没有上述方法缺点的方法。 Object of the present invention to provide a without the disadvantages of the above method a method for preparing a polyamide.该方法可以以高转换率提供聚酰胺，而且该聚酰胺的性质不会因为存在不可分离的其他组份而受到损害。 This method can provide high conversion rate polyamide and the polyamide nature does not exist because the other components can not be separated compromised.

本发明人发现通过一种制备聚酰胺的方法可以达成此目的，该方法通过任选以与氨基腈及其水解产物的混合物且任选在水的存在下反应式I的氨基羧酸化合物H2N-(CH2)mC(O)R1(I)其中R1是OH、O-C1-12烷基或NR2R3，其中R2与R3独立地为氢、C1-12烷基或C5-8环烷基，以及m是3至12的整数，该方法在作为多相催化剂的金属氧化物存在下在升高的压力和升高的温度下于液相中进行，所使用的金属氧化物形式允许机械性从反应混合物除去，并且在聚合作用期间或之后从该反应混合物中除去。 The present inventors have found that by preparing a polyamide ways to achieve this purpose, the method by optionally with the amino nitrile and its hydrolysis product of a mixture and optionally in the presence of water under reaction formula I, the amino acid compound H2N- (CH2) mC (O) R1 (I) wherein R1 is OH, O-C1-12 alkyl, or NR2R3,, wherein R2 and R3 are independently hydrogen, a C1-12 alkyl group or C5-8 cycloalkyl group, and m is an integer from 3 to 12, carried out in the liquid phase at the process in the presence of metal oxides as heterogeneous catalyst at elevated pressure and elevated temperature, the metal oxide form is used to allow mechanical mixture from the reaction It was removed, and removed from the reaction mixture during the polymerization or after.

该方法中，所使用的氨基羧酸化合物或混合物可在先前步骤中由氨基腈与水完全或不完全反应制得。 In this method, used aminocarboxylic acid compounds or mixtures may be complete or incomplete reaction of aminonitrile with water in the previous step was prepared.欲聚合的混合物中氨基羧酸化合物比例优选不少于75重量％，特别优选不少于95重量％。 Mixture to be polymerized the amino acid compound proportion is preferably not less than 75 wt%, particularly preferably not less than 95 wt%.

已发现氨基羧酸化合物或包含氨基羧酸化合物和氨基腈的混合物可以较快而且以经改良方式反应成聚酰胺。 Has been found that an amino acid compound or a mixture comprising an amino acid compounds and aminonitriles can quickly and in a through improved way reaction to the polyamide.避免使用损害该产物性质的均相催化剂。 Avoid the use of homogeneous catalyst damage the product properties.

本发明方法所使用的原料是通式I的氨基羧酸化合物H2N-(CH2)mC(O)R1(I)其中R1是OH、-O-C1-12烷基或-NR2R3，其中R2与R3独立地为氢、C1-12烷基或C5-8环烷基，且m是3、4、5、6、7、8、9、10、11或12，任选以与氨基腈的混合物使用。 The present feed process of the invention used is of the general formula I, an amino acid compound H2N- (CH2) mC (O) R1 (I) wherein R1 is OH, -O-C1-12 alkyl, or -NR2R3, wherein R2 and R3 It is independently hydrogen, a C1-12 alkyl or C5-8 cycloalkyl, and m is 3,4,5,6,7,8,9,10,11 or 12, optionally in a mixture with aminonitriles using .

该原料为市售产品，或者可如EP-A-0 234 295和Ind.Eng.Chem.Process Des.Dev.17(1978)9-16所述那样制备。 The starting material can be prepared as described in EP-A-0 234 295 and Ind.Eng.Chem.Process Des.Dev.17 (1978) The 9-16 as commercial products, or.

所使用的氨基腈原则上可为任何氨基腈，即兼具至少一个氨基和至少一个腈基的任何化合物。 The aminonitrile principle used can be any aminonitrile, i.e., both at least one amino group and any compound containing at least one nitrile group.优选ω-氨基腈，尤其是亚烷基部分具有4至12个碳原子、更优选含4至9个碳原子的ω-氨基烷基腈，或是具有8至13个碳原子的氨基烷基芳基腈，优选的氨基烷基芳基腈是芳族单元与该氨基和腈基间具有含至少一个碳原子的烷基间隔基的那些。 Preferably [omega] aminonitrile, especially alkylene moiety having 4 to 12 carbon atoms, [omega] aminoalkylnitriles more preferably having 4-9 carbon atoms or an aminoalkyl group having 8-13 carbon atoms, aryl nitrile, preferred amino alkyl aryl nitrile is an aromatic unit and the amino and nitrile group between having at least one carbon atom of the alkyl spacer of those.特别优选的氨基烷基芳基腈是该氨基与腈基互相位于1，4位置的那些。 Especially preferred aminoalkylaryl nitriles are the amino group and nitrile group is on those 4 positions each.

根据例如DE-A 836,938、DE-A 848,654或US 5,151,543所述的已知方法氢化己二腈通常制得6-氨基己腈。 The example DE-A 836,938, DE-A 848,654 or known method of US 5,151,543 hydrogenation of adiponitrile is usually obtained 6-aminocapronitrile.亦可使用多种氨基腈的混合物。 It may also be used mixtures of various aminonitrile.

用于多相催化作用的催化剂可为已知金属氧化物，诸如氧化锆、氧化铝、氧化镁、氧化铈、氧化镧和优选二氧化钛类以及用于多相催化作用的β-沸石与片状硅酸盐类。 The catalyst for the multi-phase catalysis can be known metal oxides, such as zirconium oxide, aluminum oxide, magnesium oxide, cerium oxide, lanthanum oxide and preferably titanium dioxide-based and β- zeolites and sheet-like silicon is used for multi-phase catalytic acid salts.特别优选锐钛矿多晶型物的二氧化钛。 Particularly titanium dioxide is preferably anatase polymorph thereof.另外发现硅胶、沸石和掺杂金属氧化物(掺杂剂为例如钌、铜或氟化物)可以明显改善上述原料的反应。 Also found silica gel, zeolites and doped metal oxides (dopant such as ruthenium, copper or fluoride) may significantly improve the reaction of the starting material.根据本发明，多相催化剂具有允许从催化剂机械性去除聚合物熔体(例如通过过筛或过滤)的宏观形式。 According to the present invention, a heterogeneous catalyst having allow removal of the polymer melt (e.g., by sieving or filtration) in the form of macro from the mechanical properties of the catalyst.本发明提出使用挤压物或颗粒形式或是呈在填料和/或内部构件上的涂层形式的催化剂。 The present invention proposes to use an extrudate, or granules or as a form of a coating on the filler and / or inner member catalyst.

优选使用选自β-沸石催化剂、片状硅酸盐催化剂或二氧化钛催化剂的Brnsted酸催化剂，所述的二氧化钛催化剂包括70至100重量％的锐钛矿与0至30重量％的金红石，其中最高达40重量％的二氧化钛可由氧化钨代替。 Preferably used Brnsted the acid catalyst is selected from β- zeolite catalyst, sheet-silicate catalyst or a titanium dioxide catalyst, a titanium dioxide catalyst comprising from 70 to 100 wt.% Anatase and 0 to 30% by weight of rutile, in which up to 40% by weight of titanium oxide, tungsten oxide may be replaced by.该二氧化钛催化剂中的锐钛矿比例应尽可能地高。 Anatase ratio of the titania catalyst should be as high as possible.优选使用纯锐钛矿催化剂。 Preferably using pure anatase catalyst.优选该催化剂的孔体积为0.1至5毫升/克，特别优选0.2至0.5毫升/克。 Pore ​​volume is preferably of the catalyst is from 0.1 to 5 ml / g, particularly preferably 0.2 to 0.5 ml / g.平均孔径优选在0.005至0.1微米范围内，特别优选在0.01至0.06微米范围内。 The average pore size preferably within 0.005 to 0.1 microns, particularly preferably in the 0.01 to 0.06 microns.若使用高粘度产物，平均孔径必须较大。 If the high viscosity of the product, the average pore size must be large.优选切割硬度大于20N，特别优选＞25N。 Preferably cutting hardness of greater than 20N, particularly preferably> 25N.BET表面积优选大于40平方米/克，特别优选大于100平方米/克。 BET surface area is preferably greater than 40 m2 / g, particularly preferably greater than 100 m2 / g.若BET表面积较小，必须适当提高表观体积以确保适当的催化剂活性。 If the BET surface area is small, it is necessary to appropriately increase the apparent volume to ensure adequate catalyst activity.特别优选的催化剂具有下列性质：100％锐钛矿；孔容积0.3毫升/克；平均孔径0.02微米；切割硬度32N；BET表面积116平方米/克或84重量％锐钛矿；16重量％金红石；孔容积0.3毫升/克；平均孔径0.03微米；切割硬度26N；BET表面积46平方米/克。 Particularly preferred catalysts have the following properties: 100% of anatase; pore volume 0.3 ml / g; average pore diameter of 0.02 micron; cutting hardness 32N; BET specific surface area of ​​116 m2 / g, or 84 wt% anatase; 16% by weight of rutile; pore volume 0.3 ml / g; average pore diameter of 0.03 micron; cutting hardness 26N; BET surface area 46 m2 / g.该催化剂可由市售粉末制备，例如由Degussa、Finnti或Kemira所售。 Prepared from commercially available powder of the catalyst may be, for example, sold by the Degussa, Finnti or Kemira.使用氧化钨时，最高达40重量％的二氧化钛被氧化钨替代，优选最高达30重量％，特别优选15至25重量％。 When tungsten oxide, up to 40 wt% of titanium oxide is tungsten oxide Alternatively, preferably up to 30 wt%, particularly preferably 15 to 25 wt%.可以如Ertl，Knzinger，Weitkamp：″Handbook of heterogeneous catalysis″，VCHWeinheim，1997年第98页所述制备该催化剂。 It may be as Ertl, Knzinger, Weitkamp: "Handbook of heterogeneous catalysis", VCHWeinheim, 1997 98 The catalyst was prepared.

以最大化催化剂对反应溶液所有体积元素可利用的表面积的方式将催化剂材料装填于所使用的反应容器。 In surface area manner to maximize the catalyst to the reaction solution to all volume elements available catalyst material filled in the reaction vessel to be used.若需要，可通过泵作用再循环该反应混合物以改善反应物在催化剂表面的交换作用。 If desired, the reaction mixture by a pump action recycled to improve the exchange interaction of reactants in the catalyst surface.

在固定床催化剂存在下反应该反应混合物时，该混合物的温度优选在175至350℃范围内，优选在200至300℃范围内，特别优选在230至270℃范围内。 When the reaction This reaction mixture in the presence of a fixed bed catalyst, the temperature of the mixture is preferably in the range of 175 to 350 deg.] C, preferably in the range of 200 to 300 ℃, particularly preferably in the range of 230 to 270 ℃.因为必须避免液相-固相转换，所以该温度的下限亦取决于熔体的聚合度和水含量。 Since it is necessary to avoid a liquid phase - solid phase transition, the lower limit of the temperature is also dependent on the degree of polymerization and the water content of the melt.在不存在固定床催化剂下，该反应混合物的温度在200至350℃范围内，优选在220至300℃范围内，特别优选在240至280℃范围内。 In a fixed bed catalyst is present, the reaction temperature of the mixture is in the range of 200 to 350 deg.] C, within the range of 240 to 280 deg.] C is preferably in the range of 220 to 300 ℃, particularly preferably.

本发明方法中，所提及的化合物或混合物在金属氧化物催化剂存在下且任选与水反应形成聚酰胺。 The method of the present invention, the compounds mentioned or a mixture and optionally reacted with water to form a polyamide in the presence of a metal oxide catalyst.

该方法的各具体实施方案的特征是温度-时间和压力-时间分布取决于所使用的反应物和催化剂。 Characteristics of each particular embodiment of this process is that the temperature - time and pressure - time profile reactants and catalyst depend on the used.压力和温度的时间依赖度直接取决于该反应进展、所需的分子量分布或最终产物的粘度及欲从反应混合物去除的水量。 Time dependence of pressure and temperature is directly dependent on the progress of the reaction, the desired molecular weight distribution or the viscosity of the final product and to be the amount of water from the reaction mixture removed.

方法步骤数和反应混合物中的水量取决于反应混合物的组成，尤其是取决于该反应混合物的酰胺和腈基含量。 Water method steps and the reaction mixture depending on the reaction mixture composition, in particular on the amide and nitrile group content of the reaction mixture.当该反应物不包含酰胺基和腈基，或是该反应混合物的酰胺基和腈基含量小并以原料单体为基础计优选少于30摩尔％、特别优选少于5摩尔％时，优选一步或二步实施方案。 When the reaction product does not comprise an amide group and a nitrile group, or small an amide group and a nitrile group content of the reaction mixture and to the raw material based on the monomers is preferably less than 30 mol%, particularly preferably less than 5 mol%, preferably step or two-step embodiments.当仅氨基己酸反应时，特别优选一步实施方案。 When only the aminocaproic acid reaction, particularly preferred further embodiment.若包含氨基腈和/或酰胺基的混合物反应，则特别优选三步和四步实施方案。 If contain amino nitrile and / or amide groups of reaction mixture, it is particularly preferred three-and four-step embodiment.

这样，优选含有高含量氨基己酸的混合物的缩聚作用可以按例如已知的用于己内酰胺聚合作用的连续或分步方法相似的但可使用上述较低反应温度的方法进行，其中所述方法描述于DE-A-44 13 177、DE-A-14 95 198、DE-A-25 58 480、EP-A-0 020 946及Polymerization Processes第424至467页，Interscience，纽约，1997及Handbuch der Technischen Polymerchemie第546至554页，VCH Verlagsgesellschaft，Weinheim，1993中。 Thus, preferably the polycondensation of a mixture of a high content of aminocaproic acid can be carried out, for example, but the method using the above-described lower reaction temperature continuously or similar stepwise method known for the polymerization of caprolactam action, wherein the method described in in DE-A-44 13 177, DE-A-14 95 198, DE-A-25 58 480, EP-A-0 020 946 and Polymerization Processes to 467 of 424, Interscience, New York, 1997, and Handbuch der Technischen Polymerchemie 554 pp. 546 to, VCH Verlagsgesellschaft, Weinheim, in 1993.该反应混合物的水含量特别取决于该混合物的酰胺含量。 The water content of the reaction mixture depends in particular on the amide content of the mixture.

仅使用氨基链烷酸(尤其是氨基己酸)时，优选无水时进行该反应物的反应。 When only the amino alkanoic acid (especially aminocaproic acid), preferably the reaction of the reactants when dry.

多步法为使氨基羧酸化合物和氨基腈的混合物反应，本发明方法实施方案优选有2、3或4步。 Multi-step process for the amino acid compound and an amino nitrile mixture is reacted, the method according to the present embodiment of the invention preferably have 2, 3 or 4 steps.该聚合作用可以至少三步进行，第一步是于升高的压力下进行，其中除多相催化剂之外的反应混合物以单一液相存在，且最后一步是于0.01×105至10×105帕压力下作为后缩合作用(postcondensation)进行，多相催化剂可以存在于其中的一或两个步骤中。 The polymerization may be at least three steps, the first step is carried out at elevated pressure, wherein the reaction in addition to the heterogeneous catalyst mixture is present as a single liquid phase, and the final step is to 0.01 × 105 to 10 × 105 Pa under pressure after condensation (postcondensation) as carried out, a heterogeneous catalyst may be present in which one or two steps.当酰胺和/或腈基存在于反应混合物时，特别优选具有4步的实施方案。 When the amide and / or nitrile groups present in the reaction mixture, particularly preferred embodiments having four steps.

本发明提供了一种制备聚酰胺的方法，优选连续方法，该方法通过至少任选一种为混合物形式的氨基羧酸化合物反应，该方法包括下列步骤：(1)于一个流动管中，在175至300℃温度和0.1至35×106帕压力下反应任选为混合物的氨基羧酸化合物以得到一种反应混合物，其中所述流动管可装填选自β-沸石催化剂、片状硅酸盐催化剂或二氧化钛催化剂的Brnsted酸催化剂，所述二氧化钛催化剂包括70至100重量％锐钛矿与0至30重量％金红石，其中最高达40重量％的二氧化钛可被氧化钨替代。 The present invention provides a process for preparing polyamides process, preferably a continuous method by at least choose one form of a mixture of amino acid compound, the method comprising the steps of: (1) in a flow tube, temperature of 175 to 300 deg.] C and the reaction 0.1 to 35 × 106 Pa pressure, optionally an amino acid compound of the mixture to obtain a reaction mixture, wherein the flow tube can be filled with selected β- zeolite catalyst, sheet-silicate Brnsted acid catalyst catalyst or a titanium dioxide catalyst, a titanium dioxide catalyst comprising from 70 to 100 wt.% anatase and 0 to 30% by weight of rutile in which up to 40 wt% of titanium oxide may be tungsten oxide instead.

(2)进一步于150至350℃温度和低于步骤1的压力下反应该反应混合物，该反应可在选自β-沸石催化剂、片状硅酸盐催化剂或二氧化钛催化剂的Brnsted酸催化剂存在下进行，所述二氧化钛催化剂包括70至100重量％锐钛矿和0至30重量％金红石，其中最高达40重量％的二氧化钛可被氧化钨替代，选择温度和压力应使得能获得第一气相和第一液相或第一固相或第一固相与第一液相的混合物，将第一气相从第一液相或第一固相分离或从第一液相与第一固相混合物分离，及(3)于150至370℃温度及0.1至30×106帕压力下混合第一液相或第一固相或第一固相与第一液相的混合物与包括水的气相或液相，制得一种产物混合物。 (2) further to a temperature of 150 to 350 deg.] C and below step reaction This reaction mixture under a pressure of 1, the reaction may be present Brnsted an acid catalyst is selected from β- zeolite catalyst, sheet-silicate catalyst or titanium dioxide catalyst carried out under the titanium dioxide catalyst comprising from 70 to 100 wt.% anatase and 0 to 30% by weight of rutile in which up to 40 wt% of titanium oxide may be tungsten oxide Alternatively, the temperature and pressure should be such that to obtain a first gas phase and a first liquid phase or mixture of first solid phase or a first solid phase and a first liquid phase, a first gas phase is separated from the first liquid or a first solid or a mixture of a separate phase from the first liquid phase and a first solid and (3) mixing the first mixture of liquid phase and a first liquid or first solid phase or a first solid at temperature of 150 to 370 deg.] C, and 0.1 to 30 × 106 Pa pressure comprising water vapor or liquid phase to prepare a product mixture.

前述方法优选还包括下列步骤：(4)于200至350℃温度和低于步骤3压力的压力下后缩合该产物混合物，选择温度和压力以获得含水及可能包含氨的第二气相和第二液相或第二固相或第二液相与第二固相的混合物，其均包含聚酰胺。 The method preferably further comprising the steps of: the product mixture at a pressure of (4) 3 the pressure at temperature of 200 to 350 deg.] C and below the step of the condensation, the temperature and pressure to obtain an aqueous and a second gas may include ammonia, and a second liquid or second solid phase or a second liquid phase mixture of the second solid phase which each comprise the polyamide.

所述方法步骤对应于前述步骤(1)、(2)、(3)和(4)，本方法的两步法实施方案包括步骤(1)和(4)，本方法的三步法实施方案包括步骤(1)、(2)和(4)，而本方法的四步法实施方案包括步骤(1)至(4)。 The method steps corresponding to the step (1), (2), (3) (4), the two-step embodiment of the method and the method comprises the steps (1) and (4), embodiments of the three steps of the process comprising the steps of (1), (2) and (4), while the four-step embodiment of the method comprises the steps of (1) to (4).

上述方法(即本发明步骤(1)和(4)或(1)、(2)和(4)或(1)至(4)的顺序)可间歇进行，即于单一反应器中依次进行，或是连续进行，即于连续反应器中同时进行。 The above-described process (i.e., steps of the present invention (1) and (4) or (1), (2) and (4) or (1) sequentially to (4)) may be carried out batchwise, i.e., in a single reactor sequentially, or continuously, i.e. a continuous reactor simultaneously.当然，亦可连续进行步骤(1)和(2)部分，其余步骤间歇进行。 Of course, also be carried out continuously in step (1) and (2) partially, the remaining steps batchwise.

在制备聚酰胺的本方法的另一个替代性实施方案中，于先前步骤中氨基腈与水完全或不完全反应，所得产物混合物于上述步骤(1)至(4)中进一步反应。 In another alternative embodiment of the method of preparing polyamides, in the previous step aminonitrile with water, a complete or incomplete reaction, the resulting product mixture in the above step (1) to (4) further reacted.

可以任何所需的间歇或连续步骤进行本发明的氨基腈与水的反应形成氨基己酸化合物的混合物。 It can be any desired batch or continuous steps according to the present invention, aminonitrile with water to form a mixture of aminocaproic acid compound.目的是在有或没有腈的聚合作用时实现部分水解。 Purpose is to achieve partial hydrolysis when there is polymerization or no nitrile.在适当实施方案中，可于压力容器中混合该反应混合物与水并加热。 In an appropriate embodiment, the pressure vessel mixing the reaction mixture with water and heating.氨基腈与水的摩尔比率应在1∶0.1至1∶10范围内，优选在1∶0.5至1∶6范围内，特别优选在1∶1至1∶4范围内。 Molar ratio of aminonitrile to water should be in the range of 0.1 to 1:10, preferably in the range of 0.5 to 1:6, particularly preferably in the range of 1 to 1:4.反应期间的温度应在150至300℃范围内，优选200至280℃，特别优选220至270℃范围内。 The temperature during the reaction should be in the range of 150 to 300 ℃, preferably 200 to 280 ℃, the particularly preferred range of 220 to 270 ℃.反应期间不必保持温度恒定，而且可以例如骤升(ramp)温度。 Need not be maintained during the reaction temperature constant, and may e.g. swell (RAMP) temperature.

在另一个可能的实施方案中，可以反应速率混合氨基腈与相对少量水的反应混合物与另外的水。 In another possible embodiment, may be the rate of reaction mixture aminonitrile is reacted with a relatively small amount of water was further water.此半连续过程导致相当低的自生系统压力。 This semi-continuous process results in a very low self system pressure.

本发明的反应还可于超计大气压下的连续搅拌槽中进行。 The reaction of the present invention may also be in the superatmospheric continuous stirred tank at atmospheric pressure.为此目的，该反应混合物连续计量加至搅拌槽内，同时通过压力控制阀排出反应混合物。 Purpose, the reaction for this mixture was metered continuously to a stirred tank, through the pressure control valve removed from the reaction mixture.

所有提及的过程可使用或不使用催化剂进行。 All the processes mentioned may be used with or without a catalyst.若使用催化剂，优选上述Brnsted酸金属氧化物催化剂。 If a catalyst is used, preferably above Brnsted acid metal oxide catalyst.

制得的反应产物通常为形成聚酰胺的单体与寡聚物的混合物，其比例随过程和反应条件(水含量、压力、温度)而变化。 The reaction product obtained is generally a mixture of monomer and oligomers to form a polyamide in a proportion with the procedure and the reaction conditions (water content, pressure, temperature) changes.已发现在高反应温度和反应时间或停留时间长情形下，腈基的水解作用通常更令人满意地进行。 It has been found at a high reaction temperature and reaction time or residence time long case, hydrolysis of the nitrile group is generally more satisfactorily performed.

然后可以上述多步方法将先前步骤中形成的氨基腈、氨基甲酰胺类、氨基羧酸与其他化合物的反应混合物转换成聚酰胺。 Then the multi-step method in the previous step to form the amino nitrile, carbamoyl amines, amino acids and other compounds in the reaction mixture is converted into polyamide.此反应中，于第一步中将氨基己酸化合物或其混合物与水反应，于随后反应步骤中部分水解聚合并进一步处理。 This reaction, in a first step-aminocaproic acid compound or mixtures thereof with water, in the subsequent reaction step partially hydrolyzed polymerized and further processing.整个方法包括3或4步，优选于第一和第三步中将该反应混合物形成单一液相，并将含水的液相添加于第三步中。 Overall process comprises 3 or 4 steps, preferably in the reaction of the first and third steps mixture forms a single liquid phase and the aqueous phase is added in the third step.

此外，本发明方法的内容中，亦可进行链的增长或支化或其结合。 Further, the content of the method of the present invention, can be chain growth or branched or combinations thereof.为达成此目的，可将本领域技术人员已知的聚合物支化或链增长物质添加于该反应混合物。 To achieve this object, the present skill in the art of polymer branching or chain substance is added to the reaction mixture.该物质不仅可添加于起始混合物中，亦可添加于后缩合的反应混合物中。 This material not only can be added to the starting mixture, may be added after the condensation reaction mixture.适用的物质(亦可以混合物形式使用)为：三官能的胺或羧酸作为支化剂或交联剂。 Suitable substances (also can be a mixture used) are: Trifunctional amines or carboxylic acids as branching agents or crosslinkers.至少三官能的胺或羧酸的适用实例描述于EP-A-0 345 648。 At least Suitable examples of amine or carboxylic acid trifunctional described in EP-A-0 345 648.该至少三官能的胺具有至少三个氨基，其可与羧酸基反应。 The at least trifunctional amines have at least three amino groups, which may be a carboxylic acid group reaction.其优选不具任何羧酸基。 It preferably does not have any carboxylic acid groups.该至少三官能的羧酸具有至少三个羧酸基，其可与胺反应而且亦可以例如衍生物形式(诸如酯)存在，该羧酸优选不包含任何可与羧酸基反应的氨基。 The at least trifunctional carboxylic acids have at least three carboxylic acid groups which can be reacted with the amine and also can, for example form of a derivative (such as an ester) is present, the carboxylic acid preferably does not contain any amino acid groups react with.适用的羧酸实例为苯均三酸，三聚脂肪酸，其由例如油酸制备且具有50至60个碳原子，萘多羧酸，诸如萘-1，3，5，7-四羧酸。 Suitable carboxylic Examples of trimesic acid, trimerized fatty acids, for example, 1,3,5,7-tetracarboxylic acid prepared as oleic acid and having from 50 to 60 carbon atoms, naphthalene polycarboxylic acids, such as naphthalene.该羧酸优选是定义的有机化合物且非聚合化合物。 The carboxylic acid is preferably an organic compound defined and non-polymeric compound.

优选地n是3或4，特别是3，而x是2至6的整数，优选2至4，特别是2。 Preferably n is 3 or 4, especially 3, and x is 2-6 integer, preferably 2-4, in particular 2.基团R亦可相互独立地具有所述意义。 The radicals R may each have the significance independently.优选R是一个氢原子或-(CH2)n-NH2基团。 Preferably R is a hydrogen atom or - (CH2) n-NH2 radical.

这些物质具有至少三官能基，优选至少四官能基。 These substances having at least three functional groups, preferably at least tetrafunctional.官能基数量可为3至16个，优选4至10个，特别优选4至8个。 The number of functional groups may be 3-16, preferably 4-10, particularly preferably 4-8.本发明的方法可以使用至少三官能基胺或至少三官能基羧酸进行，但是不可使用此种胺或羧酸的混合物。 The method of the present invention may use at least trifunctional amines or at least trifunctional carboxylic acid, but not mixtures of such amines or carboxylic acids used.不过，三官能基羧酸中可以存在少量三官能基胺，反之亦然。 However, the trifunctional carboxylic acid may be present in a small amount of a trifunctional amine, and vice versa.

该物质的存在量为1至50微摩尔/克聚酰胺，优选1至35，特别优选1至20微摩尔/克聚酰胺。 The substance is present in an amount of 1 to 50 mol / g of polyamide, preferably from 1 to 35, particularly preferably 1 to 20 [mu] mol / g of polyamide.该物质的存在量优选为3至150微摩尔当量/克聚酰胺，特别优选5至100微摩尔当量/克聚酰胺，特别是10至70微摩尔当量/克聚酰胺。 The presence of the substance is preferably 3 to 150 [mu] molar equivalents / g of polyamide, particularly preferably 5 to 100 micromoles equivalents / g of polyamide, in particular 10 to 70 mol equivalents / g of polyamide.该当量是以官能团氨基或羧酸数为基础计。 The equivalent is the functional groups amino, or carboxylic acid based on the number counted.

使用二官能基羧酸或二官能基胺作为链增长剂。 Difunctional carboxylic acid or a difunctional amine as chain extender.这些物质具有2个可与氨基反应的羧酸基或2个可与羧酸反应的氨基。 These substances have 2 with amino-reactive carboxylic acid groups or two reactive with a carboxylic acid group.该二官能基羧酸或胺类除羧酸基或氨基之外不包含任何可与氨基或羧酸基反应的其他官能团。 The difunctional carboxylic acids or amines other than carboxylic acid group or an amino group does not contain any other functional group reactive with an amino or carboxylic acid group.优选其不包含任何其他官能基。 Preferably it does not comprise any further functional groups.适用的二官能基胺类实例是与二官能基羧酸形成盐者。 Suitable difunctional amines Examples are forming a salt are difunctional carboxylic acids.它们可为直链脂族，诸如C1-14亚烷基二胺，优选C2-6亚烷基二胺，例如亚己基二胺。 They can be linear aliphatic, such as C1-14 alkylenediamine, preferably C2-6 alkylene diamines such as hexamethylene diamine.它们亦可为环脂族。 They may also be cycloaliphatic.它们的实例是异佛尔酮二胺、二希西坎(dicycycan)、雷罗明(laromine)。 Examples of these are isophorone diamine, Xixi Kan (dicycycan), Leiluo Ming (laromine).支链脂族二胺类同样亦适用，其实例为Vestamin TMD(三甲基六亚甲基二胺，得自Hüls AG)。 Branched chain aliphatic diamine same also applies, examples of which are Vestamin TMD (trimethyl hexamethylene diamine, from Hüls AG).它们亦可为二胺类。 They may also be diamine.整个胺可在碳骨架上被C1-12烷基取代，优选C1-14烷基。 Whole amines may be substituted with C1-12 alkyl groups on a carbon backbone, preferably C1-14 alkyl group.

该原料混合物和反应混合物可在所有阶段中与链调节剂(诸如脂族和芳族羧酸和二羧酸)和催化剂(诸如含氧的磷化合物)以0.01至5重量％范围内，优选0.2至3重量％范围内的量混合，以所使用的形成聚酰胺的单体及氨基腈数量为基础计。 The raw material mixture and the reaction mixture can be in all stages with chain regulators (such as aliphatic and aromatic carboxylic acids and dicarboxylic acid) and a catalyst (such as phosphorus, oxygen-containing compounds) in the range of 0.01 to 5% by weight, preferably 0.2 amounts to in the range of 3% by weight of the mixture, the monomers and the number of polyamide-forming aminonitrile used is based on the weight.适用的链调节剂包括例如丙酸、醋酸、苯甲酸、对苯二甲酸及三丙酮二胺。 Suitable chain regulators include for example propionic acid, acetic acid, benzoic acid, terephthalic acid and triacetonediamine.

通常于粒化之前将添加剂和填料诸如颜料、染料和稳定剂添加至反应混合物中，优选在第二、第三和第四步添加。 Typically before granulation additives and fillers such as pigments, dyes and stabilizers were added to the reaction mixture, preferably added in the second, third and fourth steps.特别优选在此过程其余部分中，该反应混合物或聚合物混合物均不与固定床催化剂接触时使用填料和添加剂。 Particularly preferably in the remainder of this procedure, the reaction mixture or a polymer mixture of fillers and additives are not in contact with the fixed bed catalyst.该组合物中可以存在一或多种经改良耐冲击橡胶作为添加剂，以整个组合物为基础计，其数量为0至40重量％，优选1至30重量％。 The composition may be present in one or more by impact rubber modified resistance as additives to the overall composition free basis, in an amount of 0 to 40 wt%, preferably 1 to 30% by weight.

可使用例如适用于聚酰胺和/或聚亚芳基醚类的常用耐冲击改性剂。 Using an impact conventional resistance modifiers such as suitable for polyamides and / or polyarylene ethers of.

这些单体可于存在或不存在诸如氢过氧化枯烯的游离基引发剂下接枝到熔体或溶液中的聚合物上。 These monomers may be in the presence or absence of a such as hydrogen peroxide, cumene hydroperoxide radical initiator at grafting to the melt or solution of the polymer.

亦可使用聚合物A下所述的α-烯烃共聚物(尤其是包括乙烯共聚物)作为替代聚合物A的橡胶，并可以照原样混合至本发明组合物中。 Also using the lower polymer A α- olefin copolymer (particularly including ethylene copolymers) as the rubber instead of polymer A, and may be as it is mixed into the composition of the present invention.

另一组适用弹性体为核-壳接枝橡胶。 Another group of suitable elastomers are core - shell graft rubbers.它们是于乳液中制得而且具有至少一种硬的与一种软的组份的接枝橡胶。 They are in the emulsion prepared and having at least one hard and a soft component group of grafted rubber.硬组份通常为玻璃化变温度至少25℃的聚合物，而软组份是玻璃化转变温度不高于0℃的聚合物。 Hard component is typically transition temperature of the glass of at least 25 deg.] C polymer, and parts of soft tissue having a glass transition temperature of the polymer 0 ℃'s.这些产物具有由核与至少一个壳形成的结构，该结构是单体加入顺序的结果。 These products have a structure formed by a core and at least one shell, the structure is a result of monomer addition order.该软组份通常衍生自丁二烯、异戊二烯、丙烯酸烷基酯、甲基丙烯酸烷基酯或硅氧烷及任选的其他共聚合单体。 Parts of the soft tissue are generally derived from butadiene, isoprene, alkyl acrylates, alkyl methacrylates or siloxanes and optionally other copolymerizable monomers.合适的硅氧烷核可制自例如环状寡聚八甲基四硅氧烷或四乙烯基四甲基四硅氧烷。 Suitable silicone approved prepared from e.g. cyclic oligomeric octamethyltetrasiloxane or tetravinyl tetramethyl siloxane.这些物质可例如于开环阳离子聚合反应中与γ-巯基丙基甲基二甲氧基硅烷反应，优选在磺酸存在下反应，形成软硅氧烷核。 These materials may be, for example, to a ring-opening cationic polymerization reaction with γ- mercaptopropyl methyl dimethoxy silane, preferably the presence of sulfonic acid to form the soft siloxane cores.亦可例如在具有可水解基团(诸如卤素或烷氧基)的硅烷(诸如四乙氧基硅烷、甲基三甲氧基硅烷或苯基三甲氧基硅烷)存在下进行聚合反应以交联该硅氧烷。 Polymerization reaction can (tetraethoxysilane, methyl trimethoxy silane or phenyl trimethoxy silane such as) the presence of silanes having hydrolyzable groups (such as halogen or alkoxy), for example, to crosslink the siloxane.此处适用的共聚单体包括例如苯乙烯、丙烯腈和具有多于一个可聚合双键的交联或接枝单体，诸如苯二甲酸二烯丙酯、二乙烯基苯、二丙烯酸丁二醇酯或(异)氰脲酸三烯丙酯。 Here Suitable comonomers include, for example, styrene, acrylonitrile, and having more than one polymerizable double bond crosslinking or grafting monomer, such as diallyl phthalate, divinyl benzene, diacrylates butylene alcohol esters or (iso) cyanurate, triallyl isocyanurate.硬组份通常衍生自苯乙烯、α-甲基苯乙烯及其共聚物，优选的共聚单体是丙烯腈、甲基丙烯腈及甲基丙烯酸甲酯。 Hard components are generally derived from styrene, alpha] -methylstyrene and copolymers thereof, preferred comonomers are acrylonitrile, methacrylonitrile and methyl methacrylate.

优选的核-壳接枝橡胶具有软核和硬壳或具有一个硬核，第一软壳和至少另外一个硬壳。 Preferred core - shell graft rubbers have a soft core and a hard shell or having a hard core, a first soft shell and at least one further hard shell.此处优选在最后的壳的聚合期间加入适当官能化的单体进行官能团的引入，该官能团为诸如羰基、羧酸、酸酐、酰胺、酰亚胺、羧酸酯、氨基、羟基、环氧基、噁唑啉、氨基甲酸酯、脲、内酰胺或卤代苄基。 Here preferably added suitably functionalized monomers during the polymerization of the last shell is introduced into a functional group, the functional group such as a carbonyl group, carboxylic acid, anhydride, amide, imide, carboxylic ester, amino, hydroxyl, epoxy , oxazoline, urethane, urea, lactam or halobenzyl group.合适的官能化单体包括例如顺式丁烯二酸、顺式丁烯二酸酐、顺式丁烯二酸一酯或二酯、(甲基)丙烯酸叔丁酯、丙烯酸、(甲基)丙烯酸缩水甘油酯及乙烯基噁唑啉。 Suitable functionalized monomers include for example maleic acid, maleic anhydride, maleic acid mono- or diesters, (meth) acrylate, t-butyl acrylate, (meth) acrylic acid glycidyl ester, and vinyl oxazoline.具有官能团的单体的比例通常在0.1至25重量％范围内，优选在0.25至15重量％范围内，其以该核-壳接枝橡胶总重为基础计。 The proportion of monomers having functional groups is generally in the range of 0.1 to 25 wt%, preferably in the range of 0.25 to 15 wt%, which is the core - graft rubber shell on the total weight based on weight.该软与硬组份的重量比例通常在1∶9至9∶1范围内，优选在3∶7至8∶2范围内。 The soft and parts hard group weight ratio is usually in the 1:9 to 9, preferably in the range of 3:7 to 8:2.

这种增强聚酰胺韧性的橡胶本身为已知的，而且描述于例如EP-A-0 208 187中。 Such reinforced polyamide toughness rubber itself is known and described, for example, in EP-A-0 208 187 in.

另一组合适的耐冲击改性剂是热塑性聚酯弹性体。 Another group of suitable impact modifiers are thermoplastic polyester elastomers.聚酯弹性体为片段化片状共聚醚酯，其包含长链片段，通常衍生自聚(亚烷基)醚二醇，及短链片段，衍生自低分子量二醇类和二羧酸类。 Polyester elastomer is a fragment of a sheet copolyetherester, comprising a long-chain segments, generally derived from poly (alkylene) ether glycols, and short-chain segments, derived from low molecular weight diols and dicarboxylic acids.这些产物为本身已知，而且描述于例如US 3,651,014等文献中。 These products are known per se and described for example in US 3,651,014 and other literature.亦有市售的相应产物，其商标为Hytrel(Du Pont)、Arnitel(Akzo)和Pelprene(Toyobo Co.Ltd.)。 Also commercially available corresponding products under the trademark Hytrel (Du Pont), Arnitel (Akzo) and Pelprene (Toyobo Co.Ltd.).

应当理解亦可使用不同橡胶的混合物。 The mixture may also use a different rubber to be understood.

可提及的其他添加剂是例如加工助剂、稳定剂与氧化抑制剂、抗热分解和抗紫外线分解剂、润滑剂和脱模剂、阻燃剂、染料和颜料及增塑剂。 Other additives may be mentioned for example processing aids, stabilizers and oxidation inhibitors, thermal decomposition and UV disintegrants, lubricants and mold release agents, flame retardants, dyes and pigments and plasticizers.其比例通常最高达40％，优选最高达15重量％，其以该组合物总重为基础计。 Which ratio is usually up to 40%, preferably up to 15 wt%, which is the total composition based on weight.

颜料和染料的存在量通常最高达4重量％，优选0.5至3.5重量％，尤其是0.5至3重量％。 Pigments and dyes generally present in amounts up to 4 wt%, preferably 0.5 to 3.5% by weight, in particular 0.5 to 3 wt%.

用以着色热塑性塑料的颜料通常为已知的，参考RGchter和H.Müller的Taschenbuch der Kunststoffadditive，Carl HanserVerlag，1983年，第494至510页。 For coloring thermoplastics pigments are generally Taschenbuch der Kunststoffadditive known reference RGchter and H.Müller of, Carl HanserVerlag, 1983 years 510 494 to.所提及的第一组优选颜料是白色颜料，诸如氧化锌、硫化锌、铅白(2 PbCO3Pb(OH)2)、锌钡白、锑白和二氧化钛。 It mentioned first group of preferred pigments are white pigments, such as zinc oxide, zinc sulfide, lead white (2 PbCO3Pb (OH) 2), lithopone, antimony white and titanium dioxide.二氧化钛的两种最常见结晶多晶型体(金红石和锐钛矿)中，优选使用金红石形式作为本发明模制组合物的白色颜料。 Two kinds of titanium dioxide is the most common crystal polymorphs (rutile and anatase), preferably as molding compositions according to the present invention, a white pigment used rutile form.

应当理解本发明可使用无机着色颜料，诸如氧化铬绿或有机着色颜料，诸如偶氮颜料和酞菁，以制得特定色彩。 It should be understood that the present invention may use inorganic coloring pigments such as chromium oxide green or organic color pigments such as azo pigments and phthalocyanines, to obtain specific colors.这些颜料通常为市售者。 These pigments are generally commercially available person.

因为上述颜料或染料的混合物(例如碳黑与铜酞菁)通常可以促进颜色于热塑性塑料中分散，所以使用该混合物具有其他优点。 Because the mixture of the pigments or dyes (e.g. carbon black and copper phthalocyanine) may generally facilitate color dispersed in a thermoplastic, so that the mixture has other advantages.

可添加于本发明热塑性材料的氧化抑制剂与热稳定剂包括例如周期表I族金属的卤化物，例如卤化钠、卤化钾、卤化锂、任选地与卤化铜(I)例如氯化物、溴化物或碘化物混合。 Can be added to the thermoplastic material of the present invention, oxidation inhibitors and heat stabilizers include, for example, a halide of the periodic table Group I metal, such as sodium halides, potassium halides, lithium halides, optionally in combination with copper (I) halide such as chloride, bromide compound or iodide mixture.该卤化物(尤其是铜的)亦可包含富电子的p配位子。 The halide (especially copper) also comprise electron-rich p-ligands seat.这种铜配合物的实例是例如带有三苯基膦的卤化铜配合物。 Examples of such copper complexes, for example with triphenylphosphine copper halide complexes.另外可使用氟化锌和氯化锌。 Further use zinc fluoride and zinc chloride.其他可能使用者为位阻酚、氢醌、其经取代的代表者、二级芳族胺，任选地与含磷的酸及其盐类混合，及这些化合物的混合物，其浓度优选最高达1重量％，以该混合物的重量为基础计。 Other possible users are sterically hindered phenols, hydroquinones, which by the representatives substituted secondary aromatic amine, optionally mixed with phosphorus-containing acids and salts thereof, and mixtures of these compounds, preferably in a concentration of up to 1% by weight, based on the weight of the mixture based on weight.

UV稳定剂的实例是各种取代的间苯二酚类、水杨酸盐类、苯并三唑类及二苯甲酮类，其用量通常最高达2重量％。 Examples of UV stabilizers are various substituted resorcinols, salicylates, benzotriazoles and benzophenones, an amount of usually up to 2 wt%.

润滑剂和脱模剂在该热塑性材料中的含量通常最高达1重量％，其为硬脂酸、硬脂醇、硬脂酸烷酯与N-烷基硬脂酰胺，以及季戊四醇与长链脂肪酸的酯类。 Content of the lubricant and release agents in the thermoplastic material is generally up to 1 wt%, which is stearic acid, stearyl alcohol, stearic acid alkyl esters with N- stearyl amide, and pentaerythritol with long chain fatty acids esters.亦可使用硬脂酸的钙、锌或铝盐以及二烷基酮类，例如二硬脂基酮。 It can also be used stearic acid, calcium, zinc or aluminum salts, and dialkyl ketones, for example distearyl ketone.

不均匀溶解于反应混合物中的物质，例如颜料和填料优选于在固定床催化剂存在下进行的制备阶段后添加到反应混合物中。 Dissolved in a mixture of non-uniform reacting, for example, pigments and fillers added to the reaction mixture, preferably after the preparation stage in the presence of a fixed bed catalyst.

本发明的聚酰胺(尤其是尼龙-6及其共聚物)可用于制备纤维、薄膜及成型物件。 Polyamide (especially nylon-6 and copolymers thereof) of the present invention may be used for preparing fibers, films and molded articles.

根据本发明，以常规方法例如利用泵将步骤3所制得的混合物或包含聚酰胺产物(优选聚合物熔体)的第二液相或第二固相或第二液相与第二固相的混合物(得自步骤4)从反应器容器排出。 According to the present invention, in a conventional manner, for example using a pump, the mixture prepared in step 3 or the second liquid phase comprises a polyamide product (preferably the polymer melt) or second solid phase or a second liquid and second solid phase mixture (from step 4) is discharged from the reactor vessel.随后，可以例如DE-A 43 21 683(第3页54行至第4页第3行)详述的常规方式后处理制得的聚合物。 Processing the resulting polymer after a conventional manner can then be, for example, DE-A 43 21 683 (page 3 line 54 to page 4 line 3) detailed.

在一优选的实施方案中，先以己内酰胺水溶液萃取然后以水萃取聚酰胺和/或对其进行气相萃取处理(描述于例如EP-A-0 284 968)可以进一步减少本发明所制得尼龙-6中的环状二聚物的量。 In a preferred embodiment, the first to-caprolactam aqueous solution was then extracted with water and extracted polyamide and / or subjected to a gas phase extraction process (described for example in EP-A-0 284 968) can be further reduced according to the present invention is prepared nylon - the amount of cyclic dimer of 6.在此后处理期间制得的低分子量组份诸如己内酰胺和其直链以及环状寡聚物可以送回第一和/或第二和/或第三步。 During the after-treatment to obtain low molecular weight component such as caprolactam and its linear and cyclic oligomers can be returned to the first and / or second and / or third step.

下列实施例用以说明本发明。 Examples are intended to illustrate the invention.

实施例样品制备和分析所谓相对粘度(PV)是分子量构成与聚合度的测量标准，其是于浓度96％硫酸中于25℃下使用Ubbelohde粘度计测量，在萃取过的材料实例中于浓度为1重量％的溶液中进行，在未萃取过的聚合物实例中于浓度为1.1重量％溶液中进行。 Examples Sample preparation and analysis of the so-called relative viscosity (PV) embodiment is a measure of molecular configuration and the degree of polymerization, which is at 25 ℃. Viscometer Ubbelohde at a concentration of 96% sulfuric acid, in the example of the material the extracted in the concentration of 1 wt carried% solution, polymer instance is not extracted through the at concentrations for 1.1 wt% solution.分析之前，未萃取过的聚合物于减压下干燥20小时。 Prior to analysis, not the extracted polymer under reduced pressure for 20 hours.

可通过酸量滴定对萃取产物测定氨基与羧酸端基的含量。 Content of the amino and carboxylic acid end groups can be determined for the product is extracted by acid titration.氨基是以使用70∶30(重量份数)酚/甲醇作为溶剂的高氯酸滴定。 Amino group is used a 70:30 (parts by weight) phenol / methanol perchloric acid titration as a solvent.羧基端基是以苄基醇作为溶剂的氢氧化钾溶液滴定。 Carboxyl end group is a benzyl alcohol solution of potassium hydroxide titrated as a solvent.

为进行萃取，于回流下，100℃搅拌100重量份聚合物混合物与400重量份去离子水32小时，然后除去水，于减压下，100℃温和地干燥(即无后缩合作用)20小时。 Is extracted, at reflux, with stirring 100 parts by weight of the polymer mixture 100 deg.] C and 400 parts by weight of deionized water for 32 hours and then water was removed under reduced pressure, 100 deg.] C gently dried (i.e., no post-condensation) 20 hours .

利用升高的压力液相色谱法(HPLC)将反应混合物分离成单个物质并分析物质级份。 Use of elevated pressure liquid chromatography (HPLC) and the reaction mixture was separated into the individual substances and analyze parts of the material level.该过程描述于Anal.Chem.43，880(1971)。 This procedure is described in Anal.Chem.43,880 (1971).先将产物溶解于水、硼酸钠缓冲剂溶液和乙腈的混合物中，用OPA衍生然后用RP18 HPLC柱分离。 First product was dissolved in a mixture of water, sodium borate buffer solution and acetonitrile with OPA derivatized and separated by RP18 HPLC column.通过一系列校正系数使浓度相关。 Through a series of correction coefficients to make relevant concentrations.

步骤催化剂颗粒是100％TiO2，其来自Finnti的S150型，呈锐钛矿形式，而且挤出物长度在2至14毫米范围内，挤出物厚度约4毫米，比表面积大于100平方米/克。 Step catalyst particles is 100% TiO2, which from Finnti of S150-type, anatase form, and the extrudate length in the 2-14 mm range, the thickness of the extrudate of about 4 mm, specific surface area greater than 100 m2 / g .

所用的氨基己腈纯度为99.5％。 Aminocapronitrile used was a purity of 99.5%.

氨基羧酸化合物的间歇反应实施例I-1在具有催化剂床或不具有催化剂床(对照用)的高压釜中进行试验，该床完全覆盖反应混合物。 Intermittent aminocarboxylic acid compound in the reaction in Example I-1 In a catalyst bed with or without a catalyst bed were tested (for comparison) autoclave, the bed completely covering the reaction mixture.与或不与催化剂一起引入氨基己酸之后，密封该高压釜，放空并以氮重复冲洗。 After without introducing aminocaproic acid catalyst with or sealing the autoclave was vented and nitrogen rinsed repeatedly.在利用阀手动控制的压力最高达18巴下加热至230℃所需反应温度1.25小时后，于1小时内将高压釜内的压力降低至环境压力(约1巴)，以致于所形成的预聚合物熔体可以进行后缩合。 After heating using the manual control valve pressure up to 18 bar at the desired reaction temperature to 230 deg.] C for 1.25 hours in 1 hour the pressure in the autoclave is reduced to ambient pressure (about 1 bar), such that the pre-formed the polymer melt can be carried out after condensation.然后将该产物以条状挤入水浴中。 The product was then stripe extruded into a water bath.

*以未萃取的产物测量将氨基腈转换成氨基羧酸混合物的先前步骤实施例II-1在一个具有加热夹套和桨式搅拌器的2升压力容器中，在一个密封反应器内于250℃搅拌1400克由氨基己腈和水(摩尔比为1∶4)组成的反应混合物。 * In unextracted product was measured to convert the amino nitrile to an amino acid mixture of the previous step in Example II-1 in a 2 liter pressure vessel having a heating jacket and a paddle stirrer at 250 in a sealed reactor the mixture ℃ stirred 1400 g of aminocapronitrile and water (molar ratio 1:4) consisting of the reaction.其自生压力为48巴。 Its autogenous pressure was 48 bar.2小时之后，氨基己腈的转换率为96.6％；该反应混合物的分析报告列于表II。 After 2 hours, the conversion of aminocapronitrile was 96.6%; the reaction mixture analysis are listed in Table II.

实施例II-2在一个具有加热夹套和桨式搅拌器的2升压力容器中，在一个密封反应器内于250℃搅拌1400克由氨基己腈和水(摩尔比为1∶1)组成的反应混合物。 Example II-2 in a 2 liter pressure vessel with heating jacket and a paddle stirrer, was stirred in a sealed reactor at 250 ℃ 1400 g of aminocapronitrile and water (molar ratio of 1) Composition reaction mixture.其自生压力为30巴。 Self-generated pressure of 30 bar.200分钟之后，氨基己腈的转换率为36％；该反应混合物的分析报告列于表II。 After 200 minutes, aminocapronitrile conversion rate of 36%; analysis of the reaction mixture is listed in Table II.

实施例II-3在一个具有加热夹套和桨式搅拌器的2升压力容器中，在一个密封反应器内于230℃搅拌1400克由氨基己腈和水(摩尔比为1∶4)组成的反应混合物。 Example II-3 in a 2 liter pressure vessel with heating jacket and a paddle stirrer, was stirred in a sealed reactor at 230 ℃ 1400 g of aminocapronitrile and water (molar ratio 1:4) Composition the reaction mixture.其自生压力为39巴。 Its autogenous pressure of 39 bar.3小时之后，氨基己腈的转换率为96％；该反应混合物的分析报告列于表II。 After 3 hours, aminocapronitrile conversion was 96%; the reaction analysis of the mixture listed in Table II.

实施例II-4在一个具有加热夹套和桨式搅拌器的2升压力容器中，在一个密封反应器内于250℃搅拌1400克由氨基己腈和水(摩尔比为1∶4)组成的反应混合物。 Example II-4 2-liter pressure vessel having a heating jacket and a paddle stirrer, was stirred in a sealed reactor at 250 ℃ 1400 g of aminocapronitrile and water (molar ratio 1:4) Composition reaction mixture.其自生压力为43巴。 Its autogenous pressure of 43 bar.于3小时反应期间，以100克/小时的流速将水连续导入该反应器。 During 3 hours the reaction, 100 g / h flow rate of water was continuously introduced into the reactor.同样地通过溢流阀自该气相中连续除去水/氨混合物。 Water / ammonia mixture was likewise continuously removed from the gas phase through the relief valve.3小时之后，氨基己腈的转换率＞99％；该反应混合物的分析报告列于表II。 After 3 hours, aminocapronitrile conversion rate> 99%; analysis of the reaction mixture is listed in Table II.

实施例II-5将包含2.7克氨基己腈、1.8克水和0.5克二氧化钛催化剂(Degussa的P25型，粗颗粒)的4.5克反应混合物加至5.5毫升容量的高压釜中。 Example II-5 comprising 2.7 g aminocapronitrile, 4.5 g of the reaction mixture was 1.8 g of water and 0.5 g titania catalyst (Degussa's P25 type, coarse particles) was added to the autoclave 5.5 ml capacity.密封该高压釜并置于250℃油浴中2小时。 The autoclave was sealed and placed in a 250 deg.] C oil bath for 2 hours.反应之后，迅速冷却该高压釜并除去反应混合物。 After the reaction, the autoclave was quickly cooled and the reaction mixture was removed.氨基己腈的转换率为约98％；该反应混合物的分析报告列于表II。 Aminocapronitrile conversion was about 98%; analysis of the reaction mixture is listed in Table II.

于一个四段中间工厂中反应在先前步骤制得的氨基羧酸化合物混合物。 Four in a pilot plant reaction mixture in an amino acid compound prepared in the previous step.原料混合物以600克/小时流速泵经第一段，其水含量为50重量％。 Starting mixture of 600 g / h flow rate of the pump through the first stage, a water content of 50 wt%.空体积为1升且内部长度1000毫米的第一段中完全装填催化剂，并于240℃温度和55巴压力下操作。 Empty volume of 1 liter and an internal length of 1000 mm in the first stage is completely packed catalyst and operating at a temperature of 240 deg.] C and 55 bar pressure.所用的第二段是2升分离容器，其中反应混合物于250℃温度和30巴压力下反应。 Used in the second stage is two liters separation vessel, wherein the reaction mixture is reacted at a temperature of 250 deg.] C and 30 bar pressure.第三段是体积为1升且长度为1000毫米装有直径6毫米且长度6毫米拉西环的流动管(反应混合物温度250℃，压力35巴)，水以流速60克/小时通过另外加热管线泵入该管中。 Third paragraph volume of 1 liter and a length of 1000 mm with a diameter of 6 mm and the flow tube length 6 mm Raschig rings (reaction mixture temperature 250 deg.] C, pressure 35 bar), the water flow rate of 60 g / hr by further heating pumped into the pipe line.第四段是由分离容器(体积2升，反应温度250℃，压力1.2巴)组成，从中利用齿轮泵以条状挤出制得的聚合物熔体。 Fourth segment by separating vessel (volume 2 liters, a reaction temperature of 250 deg.] C, pressure of 1.2 bar), with which the gear pump to the strand of the polymer melt obtained.

无催化剂时制备的聚合物用于对照。 Polymer prepared without catalyst for comparison.

表III结果：实施例II-1至II-5中先前步骤制得的氨基羧酸化合物混合物连续转换率 The results in Table III: Example II-1 to II-5 in the previous step to obtain an amino acid compound mixture is continuously conversions embodiment

Claims (6)

Translated from Chinese

1.一种制备聚酰胺的方法，其中包括反应式I的氨基羧酸化合物H2N-(CH2)m-COR1(I)其中R1是OH、O-C1-12烷基或NR2R3，其中R2和R3独立地为氢、C1-12烷基或C5-8环烷基，以及m是3至12的整数，所述化合物任选以与氨基腈及其水解产物的混合物形式进行反应，其中氨基羧酸化合物在起始混合物中的比例不少于75重量％，且反应任选在水的存在下进行，该反应是在作为多相催化剂的金属氧化物存在下，在压力为0.1至35×106帕且温度为175至350℃的液相中进行，所使用的金属氧化物形式允许其机械性地从反应混合物中除去，并且该氧化物于聚合期间或之后从该反应混合物中被除去。 1. A process for preparing a polyamide, which comprises an amino acid compound of Formula I, H2N- (CH2) m-COR1 (I) wherein R1 is OH, O-C1-12 alkyl, or NR2R3, wherein R2 and R3 is independently hydrogen, a C1-12 alkyl group or C5-8 cycloalkyl group, and m is an integer from 3 to 12, said compound optionally reacted to form the amino nitrile and its hydrolysis product mixture, wherein the amino acid ratio of the compound in the starting mixture is not less than 75 wt%, and optionally in the presence of water, the reaction is in the presence of metal oxides as heterogeneous catalyst, at a pressure of 0.1 to 35 × 106 Pa and a temperature of the liquid phase 175 to 350 deg.] C, the metal oxide form used allows it mechanically removed from the reaction mixture, and the oxide to be removed from the reaction mixture during or after the polymerization.

5.如权利要求1至3任一项的方法，其中金属氧化物催化剂与均匀溶解于反应混合物中的酸性助催化剂一起使用。 5. The method according to any one of claims 1 to 3, wherein the metal oxide catalyst homogeneously dissolved for use with an acidic co-catalyst mixture.

6.如权利要求1至3任一项的方法，其中聚合是以至少两步进行，第一步是于压力为0.1至35×106帕下进行，在该压力下除多相催化剂之外的反应混合物以单一液相存在，而后一步于0.01×105至10×105帕的压力下作为后缩合进行，所述多相催化剂可以存在于其中的一个或两个步骤中。 6. The method according to any one of claims 1 to 3, wherein the polymerization is carried out at least two steps, the first step is carried out is 0.1 to 35 × 106 Pa in pressure, at which pressure in addition to the heterogeneous catalyst the reaction mixture in a single liquid phase, and then a step to 0.01 × 105 Zhi 10 × 105 Pa pressure as a post-condensation of the heterogeneous catalyst may be present in which one or two steps.